Compounds and methods for controlling fungi, bacteria and insects

ABSTRACT

The present invention includes compounds of pyridinium salts and methods of their use for industrial uses. The present invention also relates to methods of controlling fungi and/or bacteria. The present invention may also be used to control insects.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional ApplicationNo. 60/480,995, filed on Jun. 23, 2003, U.S. Provisional Application No.60/524,775, filed on Nov. 25, 2003, U.S. Provisional Application No.60/525,075, filed on Nov. 25, 2003, U.S. Provisional Application No.60/524,784, filed on Nov. 25, 2003, and U.S. Provisional Application No.60/450,599, filed on Mar. 3, 2003, the disclosures of which areincorporated herein by reference in their entireties.

FIELD OF THE INVENTION

[0002] The present invention generally relates to methods of controllingfungi and/or bacteria. More specifically the present invention relatesto controlling fungal or bacterial infestations relating to industrialuses. The present invention may also be used to control insects.

BACKGROUND OF THE INVENTION

[0003] Vast demands exist for compounds to control microorganisms infields other than agriculture. These include the treatment of fabrics toprevent mildew and rot; to inhibit and kill bacterial growth; thetreatment of surfaces and substrates to obtain antiseptic conditions formedical, industrial, food processing and household purposes; thetreatment of wood for decking or building; the formulation of ink andpaints to prevent mold growth and bacterial decomposition; theprevention and treatment of human and animal diseases; and on through analmost infinite spectrum of applications touching our daily lives.

[0004] Fungi includes organisms such as slime molds, mushrooms, smuts,rusts, mildews, molds, stinkhorns, puffballs, truffles and yeasts. Fungiare classified in their own kingdom because they absorb food in solutiondirectly through their cell walls and reproduce through spores. Moldsare a large group of fungi that are a common trigger for allergies.Molds can exist as tiny particles called “mold spores” present in indoorand outdoor air. There are more than 100,000 species in the world. Moldsmay grow anywhere they can find moisture sources. Common molds includeCladosporium, Penicillium, Aspergillus, Alternaria, Fusarium,Stachybotyrs and Mucor.

[0005] Mold has been around forever but only recently has it began tosupport a billion dollar industry of remediation contractors,consultants, laboratories, physicians and attorneys—as evidenced by anexplosion of multi-million dollar lawsuits for property damage andpersonal injury. In Ballard v. Farmers Insurance case, a jury awarded aTexas homeowner $32.1 million, consisting of $6.2 million forremediation or replacement cost of the property damaged as well asliving expenses; $12 million in punitive damages; $5 million foremotional distress damages; and $8.9 million in attorneys' fees andcosts, for mold damage to the residence. Thus, there is a need to reducemold in buildings and homes.

[0006] There is a continuing need for new antibacterial agents. Althoughmany compounds are known which are useful in the treatment ofGram-positive and Gram-negative bacterial infections as well as othermicrobial infections, the widespread use of such compounds continues togive rise to resistant strains of microorganisms, i.e., strains ofmicroorganisms against which a particular antibiotic or group ofantibiotics, and chemical compositions which was previously effective,is no longer useful. Also, known antibiotics and chemical compositionsmay be effective against only certain strains of microorganisms or havelimited activity against either Gram-positive or Gram-negative, aerobicor anaerobic organisms.

[0007] Stilbazium iodide is a known anthelmintic which is reported to beeffective against roundworms, threadworms, and whipworms. U.S. Pat. No.3,075,975 and U.S. Pat. No. 3,085,935 recite methods of eradicatinginfestations of parasitic nematodes inhabiting the intestinal tract.

SUMMARY OF THE PRESENT INVENTION

[0008] The present invention relates to methods and compositionscomprising stilbazium. One aspect of the present invention is acomposition comprising formula (I)

[0009] or a solvate thereof wherein said compound is substantially inthe E, E configuration The amino moieties may be in either the ortho,meta or para postion. X⁻ may be an anionic salt, R₁, R₂, R₃, or R₄ areindependently selected from the group consisting of methyl, ethyl, C₁₋₁₀alkyl (linear or branched), alkenes (linear or branched), or wherein R₁and R₂ or R₃ and R₄ taken together with the nitrogen atom to which theyare attached form pyrrolidino or piperidino rings; and R₅ is selectedfrom the group consisting of methyl, ethyl, C₁₋₁₀ alkyl (linear orbranched), alkenes (linear or branched), alkynes, n-propyl, i-propyl,n-butyl, i-butyl, substituted and unsubstituted aryl moieties andsubstituted and unsubstituted benzyl moieties. The substituted andunsubstituted aryl moieties and substituted and unsubstituted benzylmoieties may include, but are not limited to lower alkyl, aryl, benzyl,acyl, amido, amino, alkoxy, carboxy, carboxy ester, alcohol, nitro,trifluoroalkoxy, trifluoroalkyl and halo. R₅ may also be anorganometallic compound such as organotin, organosilicon, ororganogermanium. Additionally, R₅ may be (CH₂)_(n)-MR₆, wherein n is anumber from 1 to 6, M is an organometallic compound such as tin,silicon, or germanium, and wherein R₆ is a selected from the groupconsisting of propyl, butyl, or any alkyl compound.

[0010] The present invention also relates to methods of controllingfungi and/or bacteria comprising administering a composition comprisingany of the below formulas or a solvate thereof.

[0011] or a solvate thereof, wherein X⁻ is an anionic salt, wherein R₁,R₂, R₃, or R₄ are independently selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl, linear or branched, alkenes, or wherein whenR₁ and R₂ or when R₃ and R₄ are taken together with the nitrogen atom towhich they are attached, they form pyrrolidino or piperidino rings. R₅is selected from the group consisting of methyl, ethyl, C₁₋₁₀ alkyl,linear or branched, alkenes, alkynes, n-propyl, i-propyl, n-butyl,i-butyl, substituted and unsubstituted aryl moieties and substituted andunsubstituted benzyl moieties. R₅ may also be an organometallic compoundsuch as organotin, organosilicon, or organogermanium. Additionally, R₅may be (CH₂)_(n)-MR₆, wherein n is a number from 1 to 6, M is anorganometallic compound such as tin, silicon, or germanium, and whereinR₆ is a selected from the group consisting of propyl, butyl, or anyalkyl compound. The present compound is more commonly known asstibazium.

[0012] The present invention also relates to methods of controllinginsects comprising administering a composition comprising any of theabove formulas or a solvate thereof.

[0013] The present invention also relates to microcapsule compositionsthat are stabilized against environmental degradation.

BRIEF DESCRIPTION OF THE DRAWINGS

[0014]FIGS. 1A-1G show various compounds including a methyl on apyridine ring at the nitrogen position.

[0015]FIGS. 2A-2G depict various compounds including a trifluoroethylattached to the pyridine ring at the nitrogen position.

[0016]FIGS. 3A-3F illustrate compounds including an isobutyl on thepyridine ring at the nitrogen position.

[0017]FIGS. 4A-4G depict various compounds with an ethyl attached to thepyridine ring at the nitrogen position.

DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION

[0018] The foregoing and other aspects of the present invention will nowbe described in more detail with respect to other embodiments describedherein. It should be appreciated that the invention can be embodied indifferent forms and should not be construed as limited to theembodiments set forth herein. Rather, these embodiments are provided sothat this disclosure will be thorough and complete, and will fullyconvey the scope of the invention to those skilled in the art.

[0019] The terminology used in the description of the invention hereinis for the purpose of describing particular embodiments only and is notintended to be limiting of the invention. As used in the description ofthe invention and the appended claims, the singular forms “a,” “an” and“the” are intended to include the plural forms as well, unless thecontext clearly indicates otherwise.

[0020] Unless otherwise defined, all technical and scientific terms usedherein have the same meaning as commonly understood by one of ordinaryskill in the art to which this invention belongs.

[0021] All publications, patent applications, patents and otherreferences cited herein are incorporated by reference in theirentireties for the teachings relevant to the sentence and/or paragraphin which the reference is presented.

[0022] The present invention relates to pyridinium derivatives,processes for their preparation, methods of their use and compositionscomprising such derivatives. Stilbazium iodide is a known anthelminticwhich is reported to be effective against roundworms, threadworms, andwhipworms. U.S. Pat. Nos. 3,075,975 and 3,085,935 recite methods oferadicating infestations of parasitic nematodes inhabiting theintestinal tract. This compound can be used to control fungi and/orbacteria for industrial uses.

[0023] One of the embodiments of the present invention includes acompound comprising:

[0024] or a solvate thereof, wherein X⁻ is an anionic salt, wherein R₁,R₂, R₃, or R₄ are independently selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), or wherein when R₁ and R₂ or when R₃ and R₄ are takentogether with the nitrogen atom to which they are attached, they formpyrrolidino or piperidino rings. X⁻ can be selected from the groupincluding fluoride, chloride, bromide, iodide halide, mesylate,tosylate, napthylate, nosylate, para-aminobenzoate, lauryl sulfate,2,4-dihydroxy benzophenone, 2-(2-hydroxy-5′-methylphenyl) benzotriazole,benzenesulfonate, besylate, ethyl 2-cyano-3,3-diphenyl acrylate and5-butyl phenyl salicylate. R₅ is selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), alkynes, n-propyl, i-propyl, n-butyl, i-butyl, substitutedand unsubstituted aryl moieties and substituted and unsubstituted benzylmoieties. R₅ may also be an organometallic compound such as organotin,organosilicon, or organogermanium. Additionally, R₅ may be(CH₂)_(n)-MR₆, wherein n is a number from 1 to 6, M is an organometalliccompound such as tin, silicon, or germanium, and wherein R₆ is aselected from the group consisting of propyl, butyl, or any alkylcompound.

[0025] Another embodiment of the present invention includes a compoundcomprising formula (II)

[0026] or a solvate thereof, wherein X⁻ is an anionic salt, wherein R₁,R₂, R₃, or R₄ are independently selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), or wherein when R₁ and R₂ or when R₃ and R₄ are takentogether with the nitrogen atom to which they are attached, they formpyrrolidino or piperidino rings. X⁻ can be selected from the groupincluding fluoride, chloride, bromide, iodide halide, mesylate,tosylate, napthylate, nosylate, para-aminobenzoate, lauryl sulfate,2,4-dihydroxy benzophenone, 2-(2-hydroxy-5′-methylphenyl) benzotriazole,benzenesulfonate, besylate, ethyl 2-cyano-3,3-diphenyl acrylate and5-butyl phenyl salicylate. R₅ is selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), alkynes, n-propyl, i-propyl, n-butyl, i-butyl, substitutedand unsubstituted aryl moieties and substituted and unsubstituted benzylmoieties. R₅ may also be an organometallic compound such as organotin,organosilicon, or organogermanium. Additionally, R₅ may be(CH₂)_(n)-MR₆, wherein n is a number from 1 to 6, M is an organometalliccompound such as tin, silicon, or germanium, and wherein R₆ is aselected from the group consisting of propyl, butyl, or any alkylcompound. The present compound is more commonly known as stibazium. Oneof the embodiments of formula I is 2,6,-bis (p-pyrrolidinostyryl)pyridine methiodide.

[0027] Alternatively, the NR₁R₂ and NR₃R₄ moieties may be in variouspositions as evidenced in the compounds below.

[0028] Another embodiment includes Formula III illustrates the NR₁R₂moiety in one meta position.

[0029] Formula IV illustrates the NR₁R₂ and NR₃R₄ moieties in both metapositions

[0030] may be an anionic salt, R₁, R₂, R₃, or R₄ are independentlyselected from the group consisting of methyl, ethyl, C₁₋₁₀ alkyl (linearor branched), alkenes (linear or branched), or wherein when R₁ and R₂ orwhen R₃ and R₄ are taken together with the nitrogen atom to which theyare attached, they form pyrrolidino or piperidino rings. R₅ is selectedfrom the group consisting of methyl, ethyl, C₁₋₁₀ alkyl (linear orbranched), alkenes (linear or branched), alkynes, n-propyl, i-propyl,n-butyl, i-butyl, substituted and unsubstituted aryl moieties andsubstituted and unsubstituted benzyl moieties.

[0031] Additionally, the present invention may include compounds of thefollowing general formula V:

[0032] or a solvate thereof, wherein n is a number from 1 to 5, whereinZ can be present at multiple positions on the phenyl ring and isselected from the group consisting of C, N, O, S and halogen, wherein X⁻is an anionic salt, wherein R₁, R₂, R₃, or R₄ are independently selectedfrom the group consisting of nothing, hydrogen, methyl, ethyl, C₁₋₁₀alkyl (linear or branched), alkenes (linear or branched), nitriles,benzenes, pyridines, benzothiophenes, trifluoroalkyls, difluoroalkyls,substituted and unsubstituted aryl moieties and substituted andunsubstituted benzyl moieties, or wherein when R₁ and R₂ or when R₃ andR₄ are taken together with the nitrogen atom to which they are attached,they form pyrrolidino or piperidino rings. X⁻ can be selected from thegroup including fluoride, chloride, bromide, iodide halide, mesylate,tosylate, napthylate, nosylate, para-aminobenzoate, benzenesulfonate,besylate, lauryl sulfate, 2,4-dihydroxy benzophenone,2-(2-hydroxy-5′-methylphenyl) benzotriazole, ethyl 2-cyano-3,3-diphenylacrylate and 5-butyl phenyl salicylate. R₅ is selected from the groupconsisting of methyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes(linear or branched), alkynes, n-propyl, i-propyl, n-butyl, i-butyl,substituted and unsubstituted aryl moieties and substituted andunsubstituted benzyl moieties. R₅ may also be an organometallic compoundsuch as organotin, organosilicon, or organogermanium. Additionally, R₅may be (CH₂)_(n)-MR₆, wherein n is a number from 1 to 6, M is anorganometallic compound such as tin, silicon, or germanium, and whereinR₆ is a selected from the group consisting of propyl, butyl, or anyalkyl compound. FIGS. 1-4 illustrate various combinations of thecompounds that may be formed according to the present invention. Thesecompounds can be in the E, E configuration and can be used for any ofthe methods and uses disclosed in the present application.

[0033] The compounds of the present invention are capable of existing asgeometric isomers. All such isomers, individually and as mixtures, areincluded within the scope of the present invention for their industrialuses. The E,E isomer is one configuration of the invention, and both thecisoid and transoid 2,6-conformations of the E,E-configuration arepossible. Additionally, the otho, ortho conformation of the structurecan be formed in addition to the para and meta structures illustratedabove. The ortho conformation structure can include the same salts andmoieties as disclosed above and throughout the application.

[0034] Some of the embodiments of the present invention include1-ethyl-(E,−E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride, 1-ethyl-(E,−E)-2,6-bis[p-(1-pyrrolidinostyryl]pyridiniumchloride,1-methyl-(E,−E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride and 1-methyl-(E,−E)-2,6-bis[p-(1-pyrrolidinostyryl]pyridiniumchloride.

[0035] Compounds according to the invention can be made according to anysuitable method of organic chemistry. More specifically, compounds offormula I can be prepared as outlined in U.S. Pat. No. 3,085,935, thedisclosure of which is incorporated in its entirety.

[0036] Additionally, embodiments of the present invention may includethe compounds produced by a synthesis that includes preparing thecompounds by condensation of two equivalents of an aldehyde of formulaIV.

[0037] with a quatenary ammonium salt of 2,6-lutidine

[0038] The condensation may be performed in a lower alcohol with acatalyst such as a secondary amine (e.g. piperidine). When X⁻ in theabove formula is an iodide ion (corresponding to an alkiodide salt oflutidine), the condensation product (formula I) is relatively insolubleand precipitates in the course of the reaction. The reaction yield offormula I can be nearly quantitative. Three times the amount of catalystas stated in U.S. Pat. No. 3,085,935 can be used. Other methods may beused to produce the compound and both more or less catalyst may beemployed to produce formula I.

[0039] Furthermore, it may be desirable to convert the iodide salt tothe chloride salt. This conversion may be accomplished by size exclusion(molecular sieve) chromatography eluted and equilibrated with a suitablesolvent containing an excess of ammonium chloride. The column effluent,containing the chloride salt can be obtained by evaporation of thesolvent, along with the ammonium iodide by-product. The resultingproduct should be substantially free of the iodide salt. Alternatively,alkchloride salt of 2,6-lutidine can be reacted with an aldehyde offormula IV in the presence of a secondary amine (e.g. piperidine) togive the chloride salt of Formula I directly.

[0040] The present invention has surprising found that the chloride salthas an increased stability as compared to the iodide salt. Other methodsknown in the art may be utilized to convert the salts to UV blockersalts or surfactant salts. Other salts may include:

[0041] Formula A—Stilbazium p-aminobenzoate salt

[0042] Formula B—Stilbazium dodecyl sulfate salt (Stilbazium laurylsulfate salt)

[0043] Additionally “salts” may include substituted benzophenones suchas 2,4-dihydroxy benzophenone, substituted benzotriazoles, such as2-(2-hydroxy-5′-methylphenyl) benzotriazole, substituted acrylates, suchas ethyl 2-cyano-3,3-diphenyl acrylate, and salicylates, such as the5-butyl phenyl salicylate.

[0044] The salts may include an ultraviolet blocker or a surfactant. Asused herein “ultraviolet blocker” refers to all “photosensitivematerials” which refers to all compositions and materials designed toblock and/or absorb ultraviolet light. This term also refers to allphotoprotective and photoresistant agents.

[0045] The compounds of the present invention may be used to treat allareas where molds, fungi and bacteria are grown. Examples include, butare not limited to wood, air ducts, lumber, decks, pipes, stucco, tiles,paint, insulation, roofs, building materials, metal, computer parts,food packaging, substrates, etc.

[0046] Another embodiment of the present invention can include thestilbazium compounds being encapsulated. As used herein the term“microcapsules” is intended to contemplate single molecules,encapsulated discrete particulate, multiparticulate, liquid multicoreand homogeneously dissolved active components. The encapsulation methodmay provide either a water soluble or oil soluble active componentencapsulated in a shell matrix of either a water or oil solublematerial. The microencapsulated active component may be protected fromoxidation and hydration, and may be released by melting, rupturing,biodegrading, or dissolving the surrounded shell matrix or by slowdiffusion of the active component through the matrix. Microcapsulesusually fall in the size range of between 1 and 2000 microns, althoughsmaller and larger sizes are known in the art.

[0047] The compound of the present invention may be placed in amicrocapsule or hollow fiber type used for distribution. They may alsobe dispersed in a polymeric material or held as a liquid.

[0048] An active ingredient may be placed with the compound of thepresent invention in a microcapsule. Examples of the active ingredienthaving repellent activity may include triethylene glycol monohexyl etherand N,N-diethyl-m-triamide. Examples of the active ingredient havingaromatic activity include geraniol, limonene, benzyl alcohol, esters ofa C₆₋₂₀ hydrocarbon, ethers, aldehydes and alcoholic compounds. Examplesof the active ingredient having pesticidal activity include insecticidessuch as salithion, diazinon and chlorpyrifos and bactericides such asthiophanate-methyl and captan.

[0049] Such constituents can be encapsulated, as is desired in the caseof phase change materials. Such encapsulated constituents can further beencapsulated in microcapsules. The microcapsules can be made from a widevariety of materials, including polyethylene, polypropylenes,polyesters, polyvinyl chloride, tristarch acetates, polyethylene oxides,polypropylene oxides, polyvinylidene chloride or fluoride, polyvinylalcohols, polyvinyl acetates, urethanes, polycarbonates, andpolylactones. Further details on microencapusulation are to be found inU.S. Pat. Nos. 5,589,194 and 5,433,953, the contents of which areincorporated herein in their entirety. Microcapsules suitable for use inthe base materials of the present invention have diameters from about1.0 to 2,000 microns.

[0050] No particular limitation is imposed on the shape for holding theactive ingredient. In other words, there are various forms for holdingthe active ingredient by a holding mixture. Specific examples includemicrocapsules in which the surface of the active ingredient has beencovered with the holding mixture; and products processed into a desiredshape, each being obtained by kneading the active ingredient in theholding mixture or forming a uniform solution of the holding mixture andthe active ingredient, dispersing the active ingredient in the holdingmixture by the removal of the solvent or the like and then processingthe dispersion into a desired shape such as single molecule, liquid,sphere, sheet, film, rod, pipe, thread, tape or chip. In addition, theseprocessed products having a surface covered with a barrier layer forcontrolling the release of the active ingredient and those coated withan adhesive for improving applicability can be given as examples. Asfurther examples, those obtained by filling the active ingredient in theholding mixture processed into a form of a capillary tube, heat sealingboth ends of the capillary tube and then encapsulating the activeingredient therein; and those obtained by centrally cutting theabove-mentioned capillary tube into two pieces, thereby having each oneend as an opening.

[0051] The container formed of a holding mixture which container has anactive ingredient enclosed therein as a liquid phase to secure uniformrelease ability over a long period of time. As such shape, tube-,bottle- or bag-shaped container is used generally.

[0052] When the mixture is formed into a container, the sustainedrelease layer desirably has a thickness of at least 0.002 mm foreffecting stable sustained release. There occurs no particular problemwhen the sustained release layer has a thickness not smaller than 0.002mm, but that ranging from 0.005 mm to 5 mm can be used. When it exceeds5 mm, the release amount of the compound tends to become too small.

[0053] For solids, the release surface area of the sustained releasepreparation formed of such a container is desirably 0.001 cm² or larger.A range of from 0.01 cm to 1 cm² may be used.

[0054] When the active ingredient is enclosed and held in a container ofthe sustained release preparation, said container having been formed ofa holding mixture, it may be enclosed in portions. The enclosed amountcan be 0.5 mg to 5 mg, and may be 1 mg, 2 mg, 3 mg, or 4 mg.

[0055] As the shape of the container formed of a holding mixture, atube, bottle and bag can be used. In the case of the tube-shapedpreparation, that having an internal diameter of 0.4 mm to 10 mm can beused. Internal diameters smaller than 0.4 mm make it difficult to fillthe active ingredient in the container, while those larger than 10 mmmake it difficult to conduct encapsulation. The bottle-shapedpreparation is formed by blow molding or injection molding and generallyhas an internal volume of 0.1 to 200 ml. The bottle having an internalvolume less than 0.1 ml cannot be formed easily, while that having aninternal volume greater than 200 ml is not economical because there is alarge difference between the amount of the active ingredient filledtherein and the internal volume. In the case of a bag-shapedpreparation, the amount of the active ingredient filled in the bag isdesirably 1 mg to 100 g.

[0056] The biodegradable sustained-release preparation according to thefirst group of the present invention should retain its essentialperformance during application so that a pigment or dye, or variousstabilizers such as ultraviolet absorber/blocker or antioxidant may beadded to the holding mixture in order to improve the weather resistance.Alternatively, it is possible to add such an additive to the activeingredient enclosed in the container formed of a holding mixture.

[0057] As used herein, the term “controlled release” is intended to meanthe release of a bio-active at a pre-selected or desired rate. This ratewill vary depending upon the application. Desirable rates include fastor immediate release profiles as well as delayed, sustained orsequential release profiles. Combinations of release patterns, such asinitial spiked release followed by lower levels of sustained release ofthe bio-active are also contemplated by the present invention.

[0058] As used herein, the term “bio-active” includes therapeutic agentssuch as pharmaceutical or pharmacological active agents, e.g., drugs andmedicaments, as well as prophylactic agents, diagnostic agents and otherchemicals or materials useful in treating or preventing conditions,infections and/or diseases. The compositions of the present inventionare particularly effective in plants and other organisms.

[0059] In accordance with the present invention there is provided amicrocapsule bacteriocide and/or fungicide composition comprisingmicrocapsules each having a polyurea shell including as an integral partof said shell a photostable ultraviolet light absorbent compound orblocker compound having a log molar extinction coefficient of from about2 to 5 with respect to radiation having wave lengths in the range offrom about 270 to 350 nanometers and a liquid fill capable of slowlypermeating the shell and comprising a pyridinium salt and a biologicalsynergist therefor.

[0060] As used herein “photosensitive material” refers to allcompositions and materials designed to block and/or absorb ultravioletlight. This term also refers to all photoprotective and photoresistantagents.

[0061] As herein used “surfactant” refers to all compositions includingsurfactant salt compositions that are capable of forming emulsions,micro-emulsions, suspensions, etc.

[0062] The entire microcapsule composition can include of 60-90 percentof liquid fill and 40-10 percent of shell wall, the liquid fillcomprising 5-40 percent of pyridinium salt, 25-50 percent of biologicalsynergist and 20-40 percent of a water-immiscible organic solvent andthe shell including as an integral part thereof 0.5-20 percent ofphotostable ultraviolet light absorbent compound (all percentages beingbased on the weight of the entire microcapsule composition).

[0063] The pyridinium salt remains inside the microcapsules while thecomposition is packaged and in storage, i.e., in a closed container dueto the partial pressure of the pyridinium salt surrounding themicrocapsules. When the product is applied as a bacteriocide and/orfungicide, the pyridinium salt, releases slowly (the actual speed ofrelease depending upon the thickness and porosity of the capsule walls).The pyridinium salt is chemically stable during storage and afterapplication until it permeates the capsule walls. At that time itbecomes available as a bacteriocide and/or fungicide until degraded.Since the fill permeates the shell wall slowly, the microcapsule producthas a long effective bacteriocide and/or fungicide life and may bestored for extended periods (e.g. for 6 months and more).

[0064] Suitable fill stabilizers absorb ultraviolet radiation in therange of about 270-350 nanometers and convert it to a harmless form.They have a high absorption coefficient in the near ultraviolet portionof the spectrum (e.g. a log molar extinction coefficient of from about 2to 5) but only minimal absorption in the visible portion of thespectrum. They do not exhibit any substantial chemical reaction with theisocyanate groups and primary amine groups of the shell formingcompounds during the microencapsulation process. Among the compoundswhich can be used as fill stabilizers are substituted benzophenones suchas 2,4-dihydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone,2-hydroxy-4-octyloxy benzophenone, etc.; the benzotriazoles such as2-(2-hydroxy-5′-methylphenyl) benzotriazole,2-(3′,5′-diallyl-2′-hydroxylphenyl)benzotriazole, etc.; substitutedacrylates such as ethyl 2-cyano-3,3-diphenyl acrylate,2-ethylhexyl-2-cyano-3,3-diphenyl acetate, etc.; salicylates such asphenyl salicylates, 5-butyl phenyl salicylate, etc.; and nickel organiccompounds such as nickel bis (octylphenol) sulfide, etc. Additionalexamples of each of these classes of fill stabilizers may be found inKirk-Othmer, Encyclopedia of Chemical Technology. The fill stabilizersmay comprise up to 5 percent, and are generally from about 0.01 to 2percent, by weight of the microcapsule composition.

[0065] The embodiments of the invention also provide a process forcontrolling fungal and bacterial activity by contacting the fungi andbacteria with an effective level of the compositions comprisingstilbazium compound as recited throughout. Contact may be accomplisheddirectly, for example, by atomization of the composition into the air inthe form of a spray. Alternatively, compositions of the presentinvention may be provided in various other forms, for example in sheetmaterials carrying the microcapsules, (e.g. tapes coated or impregnatedwith the microcapsules) that may be placed in areas where the fungi andbacteria may grow.

[0066] Another embodiment of the present invention may include heatsensitive materials which are excellent in preservation stabilityespecially in resistance to light, and microcapsules having anultraviolet absorber enclosed therein, which are applicable to variousfields. Desirable constituents which may be present in a base materialinclude materials which can absorb heat and protect an underlyingmaterial from overheating. Thermal energy is absorbed by the phasechange of such materials without causing an increase in the temperatureof these materials. Suitable phase change materials include paraffinichydrocarbons, that is, straight chain hydrocarbons represented by theformula C_(n)H_(n+2), where n can range from 13 to 28. Other compoundswhich are suitable for phase change materials are2,2-dimethyl-1,3-propane diol (DMP),2-hydroxymethyl-2-methyl-1,3-propane diol (HMP) and similar compounds.Also useful are the fatty esters such as methyl palmitate. Phase changematerials that can be used include paraffinic hydrocarbons.

[0067] Heat sensitive recording materials are well known which utilize acolor forming reaction between a colorless or light-colored basic dyeand an organic or inorganic color acceptor to obtain record images bythermally bringing the two chromogenic substances into contact with eachother. Such heat sensitive recording materials are relativelyinexpensive, are adapted for use with recording devices which arecompact and easy to maintain, and have therefore found wide applicationsas recording media for facsimile systems, various computers, etc. Inorder to improve light resistance of heat sensitive recording materialsa finely divided ultraviolet absorber or blocker can be added to theheat sensitive recording layer or protective layer.

[0068] Another embodiment of the present invention is to providemicrocapsules which have excellent retainability of ultravioletabsorber, difficult to be ruptured at a usual pressure and are excellentin ultraviolet ray absorbing efficiency.

[0069] Embodiments of the present invention can include a heat sensitiverecording material comprising a substrate, a recording layer formed overthe substrate and containing a colorless or light-colored basic dye anda color acceptor, and a protective layer formed over the recordinglayer, the recording material being characterized in that microcapsuleshaving an ultraviolet absorber enclosed therein and having substantiallyno color forming ability are incorporated in the protective layer.

[0070] Further, the present invention provides microcapsules having anultraviolet absorber and as required an organic solvent enclosedtherein, which have capsule wall film of synthetic resin and meanparticle size of 0.1 to 3 μm.

[0071] The following are examples of ultraviolet absorbers that may beused in the present invention.

[0072] Phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenylsalicylate and like salicylic acid type ultraviolet absorbers;2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone,2,2′-dihydroxy-4-methoxybenzophenone,2,2,′-dihydroxy-4,4′-dimethoxybenzophenone,2-hydroxy-4-methoxy-5-sulfobenzophenone and like benzophenone typeultraviolet absorbers; 2-ethylhexyl 2-cyano-3,3-diphenyl-acrylate, ethyl2-cyano-3,3-diphenylacrylate and like cyanoacrylate type ultravioletabsorbers; bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl) succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butyl malonate and likehindered amine type ultraviolet absorbers;2-(2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5-tert-butylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole,2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-tert -butylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-tert-butylbenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)-5-tert-amylbenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)-5-methoxybenzotriazole,2-[2′-hydroxy-3′-(3″,4″,5″,6″-tetrahydrophthalimido-methyl)-5′-methylphenyl]benzotriazole,2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-butylphenyl)benzotriazole,2-(2′-hydroxy-3′-tert-amyl-5′-phenoxyphenyl) -5-methylbenzotriazole,2-(2′-hydroxy-5′-n-dodecylphenyl)benzotriazole,2-(2′-hydroxy-5′-sec-octyloxyphenyl)-5-phenylbenzotriazole,2-(2′-hydroxy-3′-tert-amyl-5′-phenylphenyl)-5-methoxybenzotriazole,2-[2′-hydroxy-3′,5′-bis(α,α-dimethylbenzyl)phenyl]benzotriazole and likebenzotriazole type ultraviolet absorbers which are solid at ordinarytemperature; 2-(2′-Hydroxy-3′-dodecyl-5′-methylphenyl)-benzotriazole,2-(2′-hydroxy-3′-undecyl-5′-methylphenyl)-benzotriazole,2-(2′-hydroxy-3′-tridecyl-5′-methylphenyl)-benzotriazole,2-(2′-hydroxy-3′-tetradecyl-5′-methylphenyl)-benzotriazole,2-(2′-hydroxy-3′-pentadecyl-5′-methylphenyl)-benzotriazole,2-(2′-hydroxy-3′-hexadecyl-5′-methylphenyl)-benzotriazole,2-[2′-hydroxy-4′-(2″-ethylhexyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(2″-ethylheptyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(2″-ethyloctyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(2″-propyloctyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(2″-propylheptyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(2″-propylhexyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-ethylhexyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-ethylheptyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-ethyloctyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-propyloctyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-propylheptyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-propylhexyl)oxyphenyl]-benzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-butylphenyl-5-n-butylbenzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-butylphenyl)-5-tert-pentyl-benzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-butylphenyl)-5-n-pentyl-benzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-pentylphenyl)-5-tert-butylbenzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-pentylphenyl)-5-n-butylbenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-sec-butylbenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-pentylphenyl)-5-sec-butylbenzotriazole,2-(2′-hydroxy-3′-tert-butyl-5′-tert-pentylphenyl)-5-sec-butylbenzotriazole,2-(2′-hydroxy-3′,5′-di-sec-butylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-sec-butylphenyl)-5-methoxybenzotriazole,2-(2′-hydroxy-3′,5′-di-sec-butylphenyl)-5-tert-butylbenzotriazole,2-(2′-hydroxy-3′,5′-di-sec-butylphenyl)-5-n-butylbenzotriazole, octyl5-tert-butyl-3-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxybenzene-propionate,condensate of methyl3-[3-tert-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate andpolyethylene glycol (molecular weight: about 300) and like benzotriazoletype ultraviolet absorbers which are liquid at ordinary temperature. Ofcourse, the ultraviolet absorber is not limited to thereabove and can beused as required in a mixture of at least two of them.

[0073] Although the amount of ultraviolet absorber to be used is notlimited specifically, the amount can be adjusted to 10 to 500 parts byweight, and generally from to 20 to 250 parts by weight of theultraviolet absorber versus the active ingredient.

[0074] The microcapsules for use in the present invention can beprepared by various known methods. They are prepared generally byemulsifying and dispersing the core material (oily liquid) comprising anultraviolet absorber and, if necessary, an organic solvent in an aqueousmedium, and forming a wall film of high-molecular-weight substancearound the resulting oily droplets.

[0075] Examples of useful high-molecular-weight substances for formingthe wall film of microcapsules are polyurethane resin, polyurea resin,polyamide resin, polyester resin, polycarbonate resin, aminoaldehyderesin, melamine resin, polystyrene resin, styrene-acrylate copolymerresin, styrene-methacrylate copolymer resin, gelatin, polyvinyl alcohol,etc. Especially, microcapsules having a wall film of a synthetic resin,particularly polyurea resin, polyurethane resin and aminoaldehyde resinamong other resins have excellent retainability of an ultravioletabsorber and high heat resistance and accordingly exhibit theoutstanding additional effect to serve the function of a pigment whichis to be incorporated in the protective layer for preventing sticking tothe thermal head. Moreover, microcapsules having a wall film of polyurearesin or polyurethane resin are lower in refractive index thanmicrocapsules with wall films of other materials and usual pigments, arespherical in shape and are therefore usable favorably because even ifpresent in a large quantity in the protective layer, they are unlikelyto reduce the density of record images (so-called whitening) owing toirregular reflection of light. Further, polyurea resin and polyurethaneresin are more elastic than aminoaldehyde resin and therefore polyurearesin and polyurethane resin are generally used as a wall film formicrocapsules which are used under a condition of high pressure. On theother hand, microcapsules having a wall film made from aminoaldehyderesin have a merit that the wall film can be controlled in thicknesswithout depending on particle size of emulsion because the microcapsulescan be prepared by adding a wall-forming material after emulsificationof a core material.

[0076] The present invention may also include organic solvent togetherwith an ultraviolet absorber. The organic solvent is not particularlylimited and various hydrophobic solvents can be used which are used in afield of pressure sensitive manifold papers. Examples of organicsolvents are tricresyl phosphate, octyldiphenyl phosphate and likephosphates, dibutyl phthalate, dioctyl phthalate and like phthalates,butyl oleate and like carboxylates, various fatty acid amides,diethylene glycol dibenzoate, monoisopropylnaphthalene,diisopropylnaphthalene and like alkylated naphthalenes,1-methyl-1-phenyl-1-tolylmethane, 1-methyl-1-phenyl-1-xylylmethane,1-phenyl-1-tolylmethane and like alkylated benzenes, isopropylbiphenyland like alkylated biphenyls, trimethylolpropane triacrylate and likeacrylates, ester of polyol and unsaturated carboxylic acid, chlorinatedparaffin and kerosene. These solvents can be used individually or in amixture of at least two of them. Among these hydrophobic media having ahigh boiling point, tricresyl phosphate and 1-phenyl-1-tolylmethane aredesirable since they exhibit high solubility in connection with theultraviolet absorber to be used in the present invention. Generally, thelower the viscosity of the core material, the smaller is the particlesize resulting from emulsification and the narrower is the particle sizedistribution, so that a solvent having a low boiling point is conjointlyusable to lower the viscosity of the core material. Examples of suchsolvents having a low boiling point are ethyl acetate, butyl acetate,methylene chloride, etc.

[0077] The amount of organic solvent to be used should be suitablyadjusted according to the kind and amount of ultraviolet absorber to beused and the kind of organic solvent and is not limited specifically.For example in case of using an ultraviolet absorber which is liquid atordinary temperature, an organic solvent is not necessarily used.However, in case of using an ultraviolet absorber which is solid atordinary temperature, since it is desired that the ultraviolet absorberbe in a fully dissolved state in the microcapsules, the amount oforganic solvent, for example in case of microcapsules of polyurea resinor polyurethane resin, is adjusted generally from to usually 10 to 60wt. %, or from to 20 to 60 wt. %, based on the combined amount oforganic solvent, ultraviolet absorber and wall-forming material.Further, in case of microcapsules of aminoaldehyde resin, the amount oforganic solvent is adjusted to usually 50 to 2000% by weight, generallyfrom 100 to 1000% by weight of ultraviolet absorber.

[0078] Additionally, an absorber may be utilized. An absorber should beselected which reduces the sensitivity of the microcapsule in thoseportions of its spectral sensitivity range which interfere with theexposure of microcapsules at other wavelengths (its inactive range)without overly reducing the sensitivity of the microcapsule in thoseportions of the spectral sensitivity range in which the microcapsule isintended to be exposed (its active range). In some cases it may benecessary to balance the absorption characteristics of the absorber inthe active range and the inactive range to achieve optimum exposurecharacteristics. Generally absorbers having an extinction coefficientgreater than about 100/M cm in the inactive range and less than about100,000/M cm in the active range of the microcapsule are used. When theabsorber is directly incorporated into the photosensitive composition,ideally, it should not inhibit free radical polymerization, and itshould not generate free radicals upon exposure.

[0079] The absorbers used in the present invention can be selected fromamong those absorbers which are known in the photographic art. Examplesof such compounds include dyes conventionally used as silver halidesensitizing dyes in color photography (e.g., cyanine, merocyanine,hemicyanine and styryl dyes) and ultraviolet absorbers. A number ofcolored dyes which absorb outside the desired sensitivity range of themicrocapsules and do not absorb heavily within the range could also beused as absorbers in the present invention. Among these, Sudan I, SudanII, Sudan III, Sudan Orange G, Oil Red 0, Oil Blue N, and Fast GarnetGBC are examples of potentially useful compounds.

[0080] Additionally ultraviolet absorbers that may be desirable includethose selected from hydroxybenzophenones, hydroxyphenylbenzo-triazolesand formamidines. The absorbers may be used alone or in combination toachieve the spectral sensitivity characteristics that are desired.

[0081] Representative examples of useful hydroxybenzophenones are2-hydroxy-4-n-octoxybenzophenone (UV-CHEK AM-300 from Ferro ChemicalDivision, Mark 1413 from Argus Chemical Division, Witco Chem. Corp., andCyasorb UV-531 Light Absorber from American Cyanamid),4-dodecyl-2-hydroxybenzophenone (Eastman Inhibitor DOBP from EastmanKodak), 2-hydroxy-4-methoxybenzophenone (Cyasorb UV-9 Light Absorberfrom American Cyanamid), and 2,2′-dihydroxy-4-methoxybenzophenone(Cyasorb UV-24 Light Absorber from American Cyanamid). Representativeexamples of useful hydroxybenzophenyl benzotriazoles are2-(2′-hydroxy-5′-methylphenyl)benzotriazole (Tinuvin P from Ciba-GeigyAdditives Dept.),2-(3′,5′-ditert-butyl-2′hydroxyphenyl)-5-chlorobenzotriazole (Tinuvin327 from Ciba-Geigy), and 2-(2-hydroxy-5-t-octylphenyl)benzotriazole(Cyasorb UV-5411 Light Absorber from American Cyanamid). Representativeexamples of useful formamidines are described in U.S. Pat. No. 4,021,471and include N-(p-ethoxy-carbonylphenyl)-N′-ethyl-N′-phenylformamidine(Givsorb UV-2 from Givaudan Corp.). The optimum absorber andconcentration of absorber for a particular application depends on boththe absorption maximum and extinction coefficient of the absorbercandidates and the spectral sensitivity characteristics of theassociated photoinitiators.

[0082] Additionally, the microcapsules, photosensitive compositions,image-forming agents, developers, and development techniques describedin U.S. Pat. Nos. 4,399,209 and 4,440,846, the contents of which areincorporated and may be used in the present invention.

[0083] The compounds according to the present invention are alsoparticularly effective against powdery mildews and rusts, pyrenophora,rhynchosporium, tapesia, fusarium and leptosphaeria fungi, in particularagainst pathogens of monocotyledonous plants such as cereals, includingwheat and barley. They are furthermore particularly effective againstdowny mildew species, powdery mildews, leaf spot diseases and rusts indicotyledonous plants.

[0084] The amount of the compounds of the invention to be applied, willdepend on various factors such as the compound employed, the subject ofthe treatment (substrate), the type of treatment (e.g. spraying,dusting, seed dressing), the purpose of the treatment (prophylactic ortherapeutic), the type of fungi and/or bacteria to be treated and theapplication time.

[0085] The agents may be applied before or after infection of any of thematerials listed by the fungi and/or bacteria.

[0086] When applied to the plants the compound of formula I is appliedat a rate of 25 to 250 g/ha, generally from 50 to 150 g/ha, e.g. 75,100, 125 or 150 g/ha, in association with 20 to 2000 g/ha, generallyfrom 20 to 1000 g/ha.

[0087] In industrial practice the application rates of the combinationdepend on the type of effect desired, and range from 0.02 to 3 kg ofactive ingredient per hectare.

[0088] When the active ingredients are used for treating seed, rates of0.001 to 50 g a.i. per kg, and generally from 0.01 to 10 g per kg ofseed are generally sufficient.

[0089] The composition of the invention can be employed in anyconventional form, for example in the form of a twin pack, an instantgranulate, a flowable formulation, an emulsion concentrate or a wettablepowder in combination with industrially acceptable adjuvants, includingsurfactants such as sodium lauryl sulfate. Such compositions may beproduced in conventional manner, e.g. by mixing the active ingredientswith appropriate adjuvants (diluents or solvents and optionally otherformulating ingredients such as surfactants). Also conventional slowrelease formulations may be employed where long lasting efficacy isintended.

[0090] Particularly formulations to be applied in spraying forms such aswater dispersible concentrates or wettable powders may containsurfactants such as wetting and dispersing agents, e.g. the condensationproduct of formaldehyde with naphthalene sulphonate, analkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, andethoxylated alkylphenol and an ethoxylated fatty alcohol.

[0091] A seed dressing formulation is applied in a manner known per seto the seeds employing the combination of the invention and a diluent insuitable seed dressing formulation form, e.g. as an aqueous suspensionor in a dry powder form having good adherence to the seeds. Such seeddressing formulations are known in the art. Seed dressing formulationsmay contain the single active ingredients or the combination of activeingredients in encapsulated form, e.g. as slow release capsules ormicrocapsules.

[0092] In general, the formulations include from 0.01 to 90% by weightof active agent, from 0 to 20% industrially acceptable surfactant and 10to 99.99% solid or liquid adjuvant(s), the active agent consisting of atleast the compound of formula I, and optionally other active agents,particularly microbides or conservatives or the like. Concentrated formsof compositions generally contain in between about 2 and 80%, generallyfrom between about 5 and 70% by weight of active agent. Applicationforms of formulation may for example contain from 0.01 to 20% by weight,generally from 0.01 to 5% by weight of active agent. Whereas commercialproducts will generally be formulated as concentrates, the end user willnormally employ dilute formulations.

[0093] Additionally, the color of the present compounds may be removedby a type of “bleaching”. Furthermore, it has been found possible tobleach the colored substances leached from the present compound in dyedtextiles and building materials or from textiles and building materialssoiled with a colorant in a solution of wash liquor thereby preventingthe colored substance in question from being deposited on other textilesand building materials in the wash liquor, when enzymes utilizinghydrogen peroxide or molecular oxygen for the oxidation of organic orinorganic substances, including colored substances, are added to thewash liquor. Such enzymes are usually termed peroxidases and oxidases,respectively. It is well recognized in the art (cf. for instance B. C.Saunders et al., Peroxidase, London, 1964, p. 10 ff.) that peroxidasesact on various amino and phenolic compounds resulting in the productionof a color. In view of this, it must be considered surprising thatperoxidases (and certain oxidases) may also exert an effect on coloredsubstances in solution such that dye transfer is inhibited. While themechanism governing the ability of these enzymes to effect dye transferinhibition has not yet been elucidated, it is currently believed thatthe enzymes act by reducing hydrogen peroxide or molecular oxygen andoxidizing the colored substance (donor substrate) dissolved or dispersedin the wash liquor, thereby either generating a colorless substance orproviding a substance which is not adsorbed to the fabric or buildingmaterial.

[0094] Additionally, a liquid composition of matter according to thepresent invention may be formed and may be mixed with and/or diluted byan excipient. When the excipient serves as a diluent, it may be a solid,semi-solid, or liquid material that acts as a vehicle, carrier, ormedium for the composition of matter. Various suitable excipients willbe understood by those skilled in the art and may be found in theNational Formulary, 19: 2404-2406 (2000), the disclosure of pages 2404to 2406 being incorporated by reference herein in their entirety.Preferable excipients include butanedioal and EDTA. Examples of suitableexcipients include, but are not limited to, starches, gum arabic,calcium silicate, microcrystalline cellulose, methacrylates, shellac,polyvinylpyrrolidone, cellulose, water, syrup, and methylcellulose. Anaqueous medium may include an active ingredient or ingredients, aquantity of one or more surfactants sufficient to dissolve or suspendsaid active ingredients uniformly throughout the medium and othermanufacturing additives as known to the art. The latter includegranulating-binding agents such as gelatin; natural gums, such asacacia, tragacanth; starches, sodium alginate, sugars,polyvinylpyrrolidone; cellulose derivatives such ashydroxypropylmethylcellulose, polyvinyloxoazolidones; pharmaceuticalfillers such as lactose, microcrystalline cellulose, dicalciumphosphate, tricalcium phosphate, calcium sulfate, dextrose, mannitol,sucrose; tabletting lubricants if needed such as calcium and magnesiumstearate, stearic acid, talc, sterotex (alkaline stearate). The term“aqueous medium” for one ingredient of one of the embodiments of theinvention is used within the custom of the art. Primarily, it connotes awater medium, with added water-miscible solvents such as isopropanol orethanol when needed, to support the active ingredient.

[0095] The present invention is explained in greater detail in theExamples that follow. These examples are intended as illustrative of theinvention and are not to be taken are limiting thereof.

EXAMPLE 1 Synthesis of1-Ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumChloride (6)

[0096]

[0097] Step a: Reaction of 2,6-Lutidine (1) and Iodoethane (2) to Form2,6-Lutidine Ethiodide (3). A total of 69.7 grams (0.65 mole) of2,6-lutidine (1) was combined with 202.8 grams of ethyl iodide (2) andthe mixture was heated at 100° C. overnight. The reaction mixture wasthen cooled and the precipitated 2,6-lutidine ethiodide (3) wascollected by filtration. The filtrate was reheated to 100° C. overnight,then cooled and filtered to recover a second crop of solid 2,6-lutidineethiodide (3). These two crops were combined, dissolved in hot absoluteethanol and recrystallized. This resultant solid was dissolved in hotethanol and recrystallized a second time. The purified 2,6-lutidineethiodide (3) was air dried to constant weight to yield 107.5 grams ofdesired product. The ¹H-NMR was consistent with the desired material andthe uncorrected melting point was determined to be 205-206° C.

[0098] Step b: Conversion of 2,6-Lutidine Ethiodide (3) to 2,6-LutidineEthochloride (4). The 107.5 grams of 2,6-lutidine ethiodide wasdissolved in 2.0 liters of methanol and the solution was chilled in anice-water bath. A total of 220 grains of anhydrous hydrogen chloride gaswas slowly added to the solution via a gas bubbler. An ice-water bathwas used to keep the reaction temperature below 30° C. during thehydrogen chloride addition. After all the hydrogen chloride had beenadded, the reaction mixture was stirred overnight at room temperature.The reaction mixture was concentrated to near dryness and thenre-dissolved in 1.0 liter of methanol. A total of 103 grams of anhydroushydrogen chloride gas was then bubbled into the mixture. After stirringfor 10 minutes, the reaction mixture was concentrated to dryness undervacuum to yield 94.3 grams of the desired 2,6-lutidine ethochloride (4).

[0099] Step c: Reaction of 2,6-Lutidine Ethochloride (4) and4-Pyrrolidinobenzaldehyde (5) to Produce1-Ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumChloride (6).

[0100] A mixture of 30.6 grams (0.22 mole) of 2,6-lutidine ethochloride(4), 75 grams (0.54 mole) of 4-pyrrolidinobenzaldehyde (5), 12 mLpiperidine and ca. 2 liters of methanol was heated at reflux overnight.The ¹H NMR indicated that no reaction had occurred. No reaction occurredafter heating the reaction mixture for an additional 96 hours at reflux.An additional 12 mL of piperidine was added and heating at refluxcontinued. After a total of 120 hours of heating at reflux, some solidsbegan precipitating but ¹H NMR indicated that the desired reaction wasstill incomplete. Another 12 mL of piperidine catalyst was added and thereaction mixture was heated at reflux for an additional 24 hours. The ¹HNMR spectrum now indicated the desired reaction was carried tocompletion. The reaction mixture was slowly cooled to room temperatureand the precipitated solid containing1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride (6) was collected by filtration. The solid was triturated andwashed with three 100 ml portions of ethyl ether to remove impuritiesand residual methanol solvent. The solid was air dried and dried undervacuum to constant weight to yield 32.6 grams of red crystalline1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride (6)—high performance liquid chromatography area percent (HPLCArea %)=98.1%, ¹H NMR (DMSO, d6); ppm 8.16-8.14 (t,1H); 8.08-8.07(d,2H); 7.71-7.68 (d,1H); 7.69-7.67 (d,2H,J=8.8 Hz); 7.23-7.20 (d,1H);6.61-6.59 (d,2H,J=8.8 Hz); 4.75-4.74 (m,2H); 3.31 (m,2H); 1.98-1.96(m,2H); 1.48-1.45 (t,3H).

[0101] The reaction filtrate was concentrated to approximately one-halfthe original volume, 10 mL of piperidine was added and the dark reactionfiltrate was heated at reflux for 24 hours. ¹H NMR spectral analysisindicated that more1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride (6) had formed, possibly by olefinic isomer equilibration. Theheat was removed and the reaction mixture was allowed to stir at roomtemperature for 48 hours, during which time a precipitate formed. Thesolid was collected by filtration and was triturated and washed withthree 100 ml portions of ethyl ether to remove impurities and residualmethanol solvent. The red crystalline solid was air dried and driedunder vacuum to constant weight to yield 19.2 grams of additional1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride (6)—HPLC Area %=97.4%, ¹H NMR was consistent with the firstcrop of product (6).

EXAMPLE 2 Synthesis of1-Ethyl-(E,E)-2,6-bis[2-[4-(dimethylamino)phenyl]ethenyl]pyridiniumChloride

[0102]

[0103] A mixture of 9.0 grams (0.07 mole) of 2,6-lutidine ethochloride,23.6 grams (0.16 mole) of 4-dimethylaminobenzaldehyde, 14 mL piperidineand 350 mL methanol was heated at reflux for 77 hours. After 77 hr atreflux, high performance liquid chromatography—mass spectral analysis(LC/MS analysis) indicated that the desired product was present in thereaction mixture. The reaction mixture was slowly cooled to effectprecipitation and the precipitated solids were collected by filtration.The solids were triturated and washed with three 100 ml portions ofethyl ether to remove impurities and residual methanol solvent. Thesolid was air dried and dried under vacuum to constant weight to yield2.8 grams of red crystalline1-ethyl-(E,E)-2,6-bis[2-[4-(dimethylamino)phenyl]ethenyl]pyridiniumchloride—high performance liquid chromatography area percent (HPLC Area%)=99.5%, ¹H NMR (DMSO, d6) consistent with the desired product.

[0104] The reaction filtrate was concentrated to approximately one-halfthe original volume. A total of 10 mL of piperidine catalyst was addedand the dark solution was heated at reflux for an additional 24 hours.At this point high performance liquid chromatography area percentanalysis (HPLC A % analysis) indicated that more product had formed andthe 2,6-lutidine ethochloride starting material was almost gone. Theheat was removed and the reaction was concentrated under vacuum to yielda heavy slurry. The precipitated solid was collected by filtration,washed with three 100 ml portions of ethyl ether and the resulting solidwas air dried and vacuum dried overnight to yield 13.6 grams of redcrystalline1-ethyl-(E,E)-2,6-bis[2-[4-(dimethylamino)phenyl]ethenyl]pyridiniumchloride—HPLC Area %=99%, ¹H NMR was consistent with the desiredproduct.

EXAMPLE 3 Synthesis of1-Ethyl-(E,E)-2,6-bis[2-[4-(diethylamino)phenyl]ethenyl]pyridiniumChloride

[0105]

[0106] A mixture of 9.0 grams (0.07 mole) of 2,6-lutidine ethochloride,28.1 grams (0.16 mole) of 4-diethylaminobenzaldehyde, 14 mL piperidineand 350 mL methanol was heated to reflux for 96 hours at which timeLC/MS analysis indicated that the desired product was present. Thereaction mixture was cooled and concentrated under vacuum to produce aslurry. The solid was collected by filtration and was triturated andwashed with three 50 ml portions of ethyl ether. The resulting purifiedsolid was air dried and vacuum dried to yield 17.3 grams of redcrystalline1-ethyl-(E,E)-2,6-bis[2-[4-(diethylamino)phenyl]ethenyl]pyridiniumchloride—high performance liquid chromatography area percent (HPLC Area%)=95%, ¹H NMR (DMSO, d₆) was consistent with the desired material and atrace of the starting 4-diethylaminobenzaldehyde present.

EXAMPLE 4 Synthesis of1-Ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-Aminobenzoate Salt

[0107]

[0108] A total of 52.8 g (0.12 mole) of1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride and 18.6 grams (0.12 mole) of the sodium salt of 4-aminobenzoicacid (sodium salt of p-aminobenzoic acid, Na⁺ PABA⁻) were dissolved in1.3 liters of methanol and this mixture was allowed to stir at roomtemperature for 4 days during which time a precipitate formed. Thereaction mixture was then filtered and the solid salt was air dried andvacuum dried to yield a first crop of 28.0 grams of1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-aminobenzoate salt (also termed the PABA salt). The filtrate wasconcentrated under vacuum to produce more precipitate. Isolation of thesecond crop was effected by filtration followed by air drying and vacuumdrying of the solid to afford a second crop of 42.6 grams of1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-aminobenzoate salt (also termed the PABA salt)—high performance liquidchromatography area percent (HPLC A %) first crop=99.6% excluding PABA;HPLC A % second crop=99.9% excluding PABA; ¹H NMR and Mass Spectralanalyses for both crops were consistent with structure of the desiredmaterial1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-aminobenzoate salt. This product is also named1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniump-aminobenzoate salt or1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium PABAsalt.

[0109] By the methods demonstrated in Examples 1-3, substituted andunsubstituted aromatic aldehydes or substituted and unsubstitutedheteroaromatic aldehydes are reacted with substituted and unsubstitutedlutidine ethochloride salts, lutidine isobutochloride salts, lutidinemethochloride salts, lutidine 1,1,1-trifluoroethochloride salts and thelike and with secondary amine catalysts such as piperidine andpyrrolidine in polar protic solvents such as methanol, ethanol,2-propanol and the like or polar aprotic solvents such as acetonitrile(ACN), dimethyl acetamide (DMA), dimethyl formamide (DMF), dimethylsulfoxide (DMSO) and the like to yield any possible combination ofcompounds as noted throughout the application and the claims. Applicantshave additionally provided numerous compounds shown in FIGS. 1-4 toillustrate some of the possible combinations of the present invention.

[0110] In the following Examples, the “active ingredient” may be anycompound of formula (I) as recited above or a pharmaceuticallyacceptable salt or solvate thereof.

EXAMPLE 5 Antibacterial Activity

[0111] Solutions of formula I, stilbazium chloride, (1%dimethylsulfoxide) were diluted with sterile water, using serialhalf-step dilutions. Forty microliters of each dilution were thenpipetted onto seeded Mueller-Hinton agar plates. The agar plates werethen incubated for 24 hours at 35° C. and zones of inhibition were thenrecorded. The Minimum Inhibitory Concentration (MIC) was the lowestconcentration of the test material which produced a zone of inhibitionagainst the organism. The MIC for formula I against a series oforganisms is listed in the table below. TABLE 1 Anti-bacterial activityof formula I Strain MIC Streptococcus pyogenes 1.0 Streptococcusfaecalis 1.0 Streptococcus algalactia 1.0 Staphylococcus aureus 0.3Bordella bronchiseptica 1.0 Vibrio cholerae 10.0 Pasturella multocida3.0 E. coli >100 Pseudomonas aerugenosa >100

EXAMPLE 6 Antifungal Activity

[0112] Fungal strains (obtained from ATCC) were grown in Mueller-Hintonbroth for 18 hours at 35° C. Plates were then seeded with the brothculture and allowed to air-dry at room temperature (22° C.) for about10-15 minutes. Forty microliters of formula I (in 1% dimethylsulfoxide)and serial half-step dilutions in water were then pipetted onto theseeded Mueller-Hinton agar plates. The plates were then incubated for 24hours at 35° C. and zones of inhibition were then recorded. The MinimumInhibitory Concentration (MIC) was the lowest concentration of formula Iwhich produced a zone of inhibition against the organism. The followingtable lists the antifungal activity of formula I against various fungalstrains. TABLE 2 Inhibition of yeast and fungal growth by Formula I invitro Organism MIC Candida albicans <0.006 Candida tropicalis <0.4Cryptococcus neoformans <0.4 Saccharomyces cervisciae <0.4 Aspergillusfumigatus <0.006 Aspergillus flavus 6.25 Fusarium solani <0.4 Rhizopusarrihizus 6.25 Microsporidium canis 1.6 Microsporidium gypseum 1.6Trichophyton equinium 1.6 Trichophyton mentagrophyt 1.6 Trichophytonrubrum 1.6 Epidermophyton floccsum 1.6

EXAMPLE 7

[0113] Stilbazium iodide was tested against a panel of plant relevantmold stains. A stock solution of the compound was prepared in DMSO at aconcentration of 10,000 ppm a.i. Further dilutions were prepared withwater. The test was conducted at the following concentrations: 125, 31,8, 21, 0.5 and 0.125 ppm a.i. Spore suspensions of the fungi wereprepared. The test was conducted in microtiter plates and for eachfungus and each concentration, 3 wells were prepared. Incubation of theinoculated plates was carried out at 18° C. for 7 days. After this time,the optical density of the mycelium developed in each well was measuredat 405 nm.

[0114] The data produced, shown in Table 3, allowed an assessment of theIC 90 value (the concentration at which the fugal growth was reduced byat least 90% compared to the control). TABLE 3 Organism Plant RelevanceIC90 Alternaria solani Potato >125 Botrytis cinerea Vegetable 0.5Cochliobolus mijabeanus Corn >125 Colletotrichum lagenarium Mellons 31Fusarium culmorum Wheat Head >125 Phytophthora infestans Tomato 2Pyrenophora teres Barley 31 Pyricularia oryzae Rice 8 Rhizoctonia solaniRice Sheath 2 Septonia tritici Wheat Leaf 2

EXAMPLE 8

[0115] The data shown below in Table 4 illustrates various bacteria andfungi that can be treated by stilbazium compounds. The data illustratesthe overall effectiveness of various stilbazium compounds. TABLE 4 MICMIC Species Isolate # 80% 100% MFC Alternaria species 128.89 6.2512.5 >100 Aspergillus flavus 112.96 3.12 6.25 6.25 Aspergillus flavus194.99 3.12 3.12 12.5 Aspergillus flavus 107.96 6.25 12.5 25 Aspergillusflavus 141.88 12.5 25 25 Aspergillus flavus 178.03 12.5 25 >25Aspergillus flavus 173.03 25 25 >25 Aspergillus fumigatus 168.95 3.126.25 >25 QC A. fumigatus 168.95 3.12 6.25 >100 QC A. fumigatus 168.953.12 6.25 >100 Aspergillus fumigatus 111.02 3.12 6.25 12.5 Aspergillusfumigatus 153.90 12.5 25 25 Aspergillus fumigatus 182.99 12.5 25 >25Aspergillus sydowii 165.02 0.78 1.56 3.12 Aspergillus versicolor 120.021.56 3.12 6.25 Bipolaris spicifera 155.89 3.12 3.12 >100 Candidaalbicans A39 0.39 0.39 0.39 Candida albicans 117.00 0.39 0.39 0.39 QC C.albicans 117.00 1.56 1.56 3.12 QC C. albicans 117.00 3.12 3.12 6.25Candida albicans 117.00 0.78 1.56 3.12 Candida albicans 116.98 0.39 0.391.56 Candida albicans 126.97 0.39 0.78 0.78 Candida albicans 149.97 0.390.39 0.78 Candida albicans 159.95 0.39 0.39 1.56 Candida albicans 156.971.56 1.56 1.56 Candida albicans 203.03 1.56 1.56 3.12 Candida albicans204.03 1.56 1.56 1.56 Candida albicans 205.03 1.56 1.56 6.25 Candidaalbicans 206.03 3.12 3.12 12.5 Candida albicans 202.03 3.12 3.12 3.12Candida parapsilosis 110.01 0.78 0.78 3.12 Candida parapsilosis ATCC22019 0.78 0.78 3.12 Candida parapsilosis 109.96 1.56 1.56 3.12 Candidaparapsilosis 118.02 1.56 1.56 6.25 Candida parapsilosis 123.00 1.56 1.566.25 Chaetomium species T 217 1.56 3.12 >100 Cryptococcus neoformans H990.012 0.024 1.56 Curvularia lunata 141.90 1.56 3.12 >100 Curvularialunata 110.90 3.12 3.12 >100 Curvularia lunata v. aeria 104.89 3.126.25 >100 Curvularia lunata 146.90 6.25 6.25 >100 Penicillium 135.026.25 12.5 >100 aurantiogriseum Penicillium chrysogenum 119.02 0.78 0.7812.5 Rhizopus oryzae 172.86 1.56 6.25 >100 Rhizopus oryzae 182.88 3.126.25 >100 Rhizopus oryzae 318.86 3.12 6.25 >100 Rhizopus oryzae 117.896.25 6.25 12.5 Rhizopus oryzae 127.88 12.5 12.5 >25 Rhizopus oryzae181.88 12.5 12.5 >25 Rhodotorula mucilaginosa 213.03 1.56 3.12 6.25Rhodotorula mucilaginosa 207.03 3.12 3.12 3.12 Rhodotorula mucilaginosa209.03 3.12 6.25 6.25 Rhodotorula mucilaginosa 210.03 3.12 3.12 3.12Rhodotorula mucilaginosa 211.03 6.25 6.25 6.25

[0116] In the specification, there has been disclosed typical preferredembodiments of the invention and, although specific terms are employed,they are used in a generic and descriptive sense only and not forpurposes of limitation of the scope of the invention being set forth inthe following claims.

What is claimed is:
 1. A compound comprising:

or a solvate thereof and wherein said compound is in an E, Econfiguration; wherein the NR₁R₂ and NR₃R₄ moieties are in the ortho,meta or para position; wherein X⁻ is an anionic salt; wherein R₁, R₂,R₃, or R₄ are independently selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), or wherein R₁ and R₂ or R₃ and R₄ taken together with thenitrogen atom to which they are attached form pyrrolidino or piperidinorings; and wherein R₅ is selected from the group consisting of methyl,ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear or branched),alkynes, n-propyl, i-propyl, n-butyl, i-butyl, substituted andunsubstituted aryl moieties and substituted and unsubstituted benzylmoieties.
 2. The compound of claim 1, wherein X⁻ is selected from thegroup consisting of fluoride, chloride, bromide, iodide halide,mesylate, tosylate, napthylate, nosylate, para-aminobenzoate, laurylsulfate, 2,4-dihydroxy benzophenone, 2-(2-hydroxy-5′-methylphenyl)benzotriazole, benzenesulfonate, besylate, ethyl 2-cyano-3,3-diphenylacrylate and 5-butyl phenyl salicylate.
 3. The compound of claim 1,wherein R₅ is (CH₂)_(n)-MR₆, wherein n is a number from 1 to 6, M is anorganometallic compound selected from the group consisting of tin,silicon, and germanium, and wherein R₆ is a selected from the groupconsisting of propyl, butyl, and alkyl, substituted or unsubstituted. 4.The compound of claim 1, wherein said compound is selected from thegroup consisting of1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(dimethylamino)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(diethylamino)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-aminobenzoate salt and1-methyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride, substantially free of any other configurational isomers.
 5. Amethod of combating fungi and/or bacteria in wood, air duct, paint,sheetrock, food packaging, or food products, wherein said methodcomprises administering to said wood, air duct, paint, sheetrock, foodpackaging, or food product an effective amount of the compound ofclaim
 1. 6. A method for treating an industrial product with fungalgrowth that comprises administering to the site where growth is to betreated an effective amount of the compound of claim
 1. 7. A compositioncomprising:

or a solvate thereof and wherein said compound is in an E, Econfiguration; wherein the NR₁R₂ and NR₃R₄ moieties are in the ortho,meta or para position; wherein X⁻ is an anionic salt; wherein R₁, R₂,R₃, or R₄ are independently selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), or wherein R₁ and R₂ or R₃ and R₄ taken together with thenitrogen atom to which they are attached form pyrrolidino or piperidinorings; and wherein R₅ is selected from the group consisting of methyl,ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear or branched),alkynes, n-propyl, i-propyl, n-butyl, i-butyl, substituted andunsubstituted aryl moieties and substituted and unsubstituted benzylmoieties; and an excipient.
 8. A synthetic process for preparing thecomposition according to claim 7 comprising administering HCl to thecomposition.
 9. The composition of claim 7, wherein X⁻ is selected fromthe group consisting of fluoride, chloride, bromide, iodide halide,mesylate, tosylate, napthylate, nosylate, para-aminobenzoate, laurylsulfate, 2,4-dihydroxy benzophenone, 2-(2-hydroxy-5′-methylphenyl)benzotriazole, benzenesulfonate, besylate, ethyl 2-cyano-3,3-diphenylacrylate and 5-butyl phenyl salicylate.
 10. The composition of claim 7,wherein said compound is wherein said composition is selected from thegroup consisting of1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(dimethylamino)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(diethylamino)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-aminobenzoate salt and1-methyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride, substantially free of any other configurational isomers.,substantially free of any other configurational isomers.
 11. Thecomposition of claim 7, wherein R₅ is (CH₂)_(n)-MR₆, wherein n is anumber from 1 to 6, M is an organometallic compound selected from thegroup consisting of tin, silicon, and germanium, and wherein R₆ is aselected from the group consisting of propyl, butyl, and alkyl,substituted or unsubstituted.
 12. The composition of claim 7 furthercomprising a fungicide and/or bacteriocide.
 13. The composition of claim7 further comprising an insecticide.
 14. The composition of claim 7,wherein said composition is encapsulated in an emulsion or amicroencapsule.
 15. The composition of claim 14, wherein saidmicrocapsule is a time-release capsule.
 16. The composition of claim 7,wherein said composition is in a sustained release form or in anon-sustained release form.
 17. A method of controlling fungi and/orbacteria comprising administering a composition comprising:

or a solvate thereof and wherein the NR₁R₂ and NR₃R₄ moieties are in theortho, meta or para position; wherein X⁻ is an anionic salt; wherein R₁,R₂, R₃, or R₄ are independently selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), or wherein R₁ and R₂ or R₃ and R₄ taken together with thenitrogen atom to which they are attached form pyrrolidino or piperidinorings; and wherein R₅ is selected from the group consisting of methyl,ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear or branched),alkynes, n-propyl, i-propyl, n-butyl, i-butyl, substituted andunsubstituted aryl moieties and substituted and unsubstituted benzylmoieties.
 18. The method according to claim 17, wherein said method ofcontrolling fungi and/or bacteria further comprises binding andcontaining the fungi and/or bacteria in the same area.
 19. The methodaccording to claim 17, wherein said composition is administered beforefungal growth occurs.
 20. The method according to claim 17, wherein R₅is (CH₂)_(n)-MR₆, wherein n is a number from 1 to 6, M is anorganometallic compound selected from the group consisting of tin,silicon, and germanium, and wherein R₆ is a selected from the groupconsisting of propyl, butyl, and alkyl, substituted or unsubstituted.21. The method according to claim 17, wherein said composition isadministered after fungal growth occurs.
 22. The method according toclaim 17, wherein said composition is administered to a substrate. 23.The method according to claim 22, wherein said substrate is selectedfrom the group consisting of sheetrock, lumber, decking, flooring,roofing, carpets, wallpaper, paneling, cloth caulking, mortar, tiles,grout, fasteners, adhesives, paint, coatings, sealants and stucco. 24.The method according to claim 17, wherein said method comprisescontrolling fungi and/or bacteria by reducing fungal and/or bacterialgrowth in food packaging systems.
 25. The method according to claim 17,wherein said method comprises controlling fungi and/or bacteria inmedical products.
 26. The method according to claim 24, wherein saidfood packaging system are selected from the group consisting of plastic,paper and foam.
 27. The method according to claim 17, wherein saidmethod further comprises administering organotin, organosilicon, ororganogermanium.
 28. The method according to claim 17, wherein R₅ is anultraviolet blocker or an ultraviolet absorber.
 29. The method accordingto claim 28, wherein said ultraviolet blocker or an ultraviolet absorberis selected from the group consisting of

and H₃C(H₂C)(H₂C)₁₀—O—SO₃ ⁻Na⁺.
 30. A microcapsule comprising acomposition comprising formula (I)

or a solvate thereof and wherein the NR₁R₂ and NR₃R₄ moieties are in theortho, meta or para position; wherein X⁻ is an anionic salt; wherein R₁,R₂, R₃, or R₄ are independently selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), or wherein R₁ and R₂ or R₃ and R₄ taken together with thenitrogen atom to which they are attached form pyrrolidino or piperidinorings; wherein R₅ is selected from the group consisting of methyl,ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear or branched),alkynes, n-propyl, i-propyl, n-butyl, i-butyl, substituted andunsubstituted aryl moieties and substituted and unsubstituted benzylmoieties; an excipient; and a photosensitive material.
 31. Themicrocapsule of claim 30, wherein the photosensitive material absorbsultraviolet radiation.
 32. The microcapsule of claim 30, wherein thephotosensitive material blocks ultraviolet radiation.
 33. Themicrocapsule of claim 30, wherein a ratio of the photosensitive materialto the formula is 1:10.
 34. A method of controlling insects comprisingadministering a composition comprising formula (I)

or a solvate thereof and wherein the NR₁R₂ and NR₃R₄ moieties are in theortho, meta or para position; wherein X⁻ is an anionic salt; wherein R₁,R₂, R₃, or R₄ are independently selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), or wherein R₁ and R₂ or R₃ and R₄ taken together with thenitrogen atom to which they are attached form pyrrolidino or piperidinorings; and wherein R₅ is selected from the group consisting of methyl,ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear or branched),alkenes, alkynes, n-propyl, i-propyl, n-butyl, i-butyl and benzylradicals.
 35. The method according to claim 34, wherein said compositionis administered to wastewater.
 36. A compound comprising:

or a solvate thereof, and wherein n is a number from 1 to 5; wherein Zis selected from the group consisting of C, N, O, S and halogen; whereinthe ZR₁R₂ and ZR₃R₄ moieties are in the ortho, meta or para positions;wherein X⁻ is an anionic salt; wherein R₁, R₂, R₃, or R₄ areindependently selected from the group consisting of nothing, hydrogen,methyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), or wherein R₁ and R₂ or R₃ and R₄ taken together with thenitrogen atom to which they are attached form pyrrolidino or piperidinorings; and wherein R₅ is selected from the group consisting of methyl,ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear or branched),alkynes, n-propyl, i-propyl, n-butyl, i-butyl, substituted andunsubstituted aryl moieties and substituted and unsubstituted benzylmoieties, with the provisio that said compound is not 1-ethyl-(Z,Z),(Z,E) or (E,Z)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride.
 37. The compound of claim 36, wherein said compound is in anE, E configuration.